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Patented July 26, 1949 TE A E PATENT; OFFICE QABYLOXYALKENES McBee, La Fayette, Ind., and Robert O.

Bolt,"Richmond, Calif., assignprs to Purdue l Research Foundation, La Fayette, Ind., a. 001'? notation of Indiana N o Drawing.

Application Septemberll, 1946,

4 Claims. (c1. 261F612) j tainingup to 2 carbonzatoms, inclusive. These compoundsare usefulas heat-transfer media and as chemical intermediates. l

The compounds may be prepared by the dehalogenation of the corresponding halogenated aryloxyalkanes by' meansof a suitable dehalogenatingl agent, e. g.,'zinc'1 in ethanolror by the dehy drohalogenation of" a "suitable halogenated aryloxyalkane by means of an appropriate dehydrohalogenating agent, e. g; aqueous sodium hydroxide solution, 4 They may also be synthesized by condensing a suitablealkali hmetal aryloxide or substitutedaryloxide, e. g. sodium phenoxide, sodium methylphenoxide; sodium trifiuoromethylphenoxide, sodium napthoxide, et cetera, and a polytchlorofluoro)alkane,. e. g, 1,2-di chloro-. Ll-IdifluoroethaheQ .l,2,2-trichloro-1;1-difluoroethane, 2 chloro-.1,1,1,3,3,3 hexafluoro propane, .etlcetra, at low or. moderatetemperaa to a group of novel comalkyl .or halogen-substituted alkyl radical conwas then steam distilled, andthe lower layer of the distillateseparated and dried. Rectification of this organic product yielded 0.15 mole of phenoxy-2-chloro-1-fluoroethene, boiling at 57.2 to 57.3 degrees centigrade at six millimeters of mercury pressure absolute.

Anhydrous sodium 3 methylphenoxide (2 moles) and: a small amount of toluene. were dissolved in a liter ofanhydrous acetone a flaskfltted with sealed stirrer, reflux condenser and thermometen- The mixture was cooled to '7 de-. grees centigrade by means of an ice bathjand two. :moles (2'70 grams) of 1,2-.dichloro-1,1-difiuoroetha'nei was added with constantagitation overa two-hour period. .No temperature increase occurred during the addition. The reac tion-mixture was, warmed to room temperature turaior example, zero to 15 0 degrees centigrade,

in an acetone or other nonreactive solvent medium and recovering theproduct from a basic reaction mixture by steam distillation followed by drying and rectification of the organic. layer of the distillate. In some cases it may be necessaiy to employ the more. reactive potassiumarylw oxide, and thereaction medium may be selected to} allowfl optimum solubility of the particular aryloxidewand poly(chlorofiuoro) alkane ,con cerned in the reaction A preponderance of the halogenated aryloxyalkane, from which the halogenated aryloxyalkane may be considered as heing derivedby dehalogenatio-n or dehydrohalogenation, is usually also formed in any particular condensation reaction. 1

The following examples illustrate several Ways inwhich members of the new group of compounds may be prepared, but are not to be construed as limiting l H J l l EXAMPLE 1 .Phenoxy 2,2; dichloro- 11,1 difluoroethane (0.22 mole),f0.78 mole of zinc powder and 150 milliliters of per centethanolwere mixed in' a flasktfitted with a sealed-stirrer, reflux condenser and thermometer. The temperature was maintained at reflux, about 78 degrees centigrade, and constant stirring was employed over a pe-. riod of thirty-three hours. The reaction mixture and finally heated for 12 hoursat 40-50 degrees centigrad'e. Acetone was then stripped from the mixture and after the-residue was made basic (pl-I 9), steam distillation was used to remove organic reaction products. The organic layer of the distillate was separated, dried withsodium sulfate, and then rectified. rThe-fractionboiling at 64.0-64.4 degrees centigrade ,at 4.0 millimeters of mercury pressure absolute was identified as (3 methylphenoxy) -:2 chloro-l-fluoroethene. The majority o'f the'product was identified .as (3 methylphenoxyy- 2e chloro-Ll-difluoroethanelq 1 i m refluxed gently for about 1'7 hours, at the end of "which time the reflux condenser was arranged to allow distillation. About 800 milliliters of or ganic material distilled, and after two moles of dilute sodium hydroxide had been added to the residue, an additional amount of organic matter was steam-distilled. Thedistillates were sepa j rately washed withwater and .the organic layers separated and dried over calcium chloride. A considerable, f amount of Z CmOIO-lJ-(iifillOI 'O- ethane (0.59 mole) was collected in the pry-Icecooled trap during, this experiment. Rectifica:

tion of the combined organic productsofthere;

action in a column developing theoretical plates atw atmospheric pressure yielded Q- physical constants of some of the compounds of 10 the present invention.

X is selected from the group consisting of Cl and F; and wherein Y is selected from the group consisting of H, Cl, F and alkyl and halogen-substituted alkyl radicals, the alkene group 5 containing up to two carbon atoms, inclusive.

2. Phenoxy-2,2-dichloro-l-fluoroethene. 3. Phenoxy-z-chloro-l-fluoroethene. 4. Phenoxy 2 chloro 1,3,3,3-tetrafluoropropene.

EARL T. McBEE. ROBERT O. BOLT.

Tum:

Certain aryloxv (polychlorofluoromlkenes Analyses Formula M r o D N w c 1 'a t F a 744 MM. 4 D a 0 P810911 011.11 136F001;

01 F M. w. 01 F M. w.

o.n.oor=oo1, 210.0 -42.0 to 44. 5 1.3364 1. 5162 34.3 9.2 207 34. 2 9.0 206 CoHiOCF=CHG1 189.5 50.0 to --51.0 1.2271 1. 5049 20. 5 11.0 172. 5 20. 3 11.7 172 2-CH;C H 0CF=CHCL 204. 5 38. 5 to -39.0 1.1903 1. 5057 19. 0 l0. 2 186. 5 18. 9 10. 6 185 3-CH;O H OCF=OHG1 209. 0 Sets to glass 1. 1880 1. 5031 19.0 10.2 186. 5 18. 7 l0. 5 186 4-CH;C H OCF=CHC1--- 212.5 -40.0 to 41. 5 1. 1854 1. 5032 19.0 10.2 186. 5 18.8 10.7 185 3'OF3CQH4 OOF=CHCL 189. 5 -03.0 to 64.0 1.3409 1.4454 14.8 31.6 240.5 14.4 32.6 243 OaHaOGF=OC1C 184. 5 -53.0 to -56.0 1. 3673 1. 4513 14. 8 31. 6 240. 5 14. 1 31. 4 236 1.Q H (A) OOF=CO1 CE- 275.0 10.5 to 13.0 1.3859 1. 5295 12.2 26. 1 290. 5 12. 8 27. 3 284 A Naphthyl.

Various modifications may be made in the pres- 30 wherein R is selected from the group consisting of phenyl and naphthyl radicals; Z is selected from the group consisting of CH: and CFs; n is selected from the group consisting of 0, 1 and 2;

35 Number REFERENCES CITED The following referemces are of record in the file of this patent:

UNITED STATES PATENTS Name Date 2,409,274 Hanford Oct. 15, 1946 FOREIGN PATENTS Number Country Date Great Britain July 15, 1940 

